Molding powder and process of making the same



Patented Oct. 6, 1936 UNITED STATES PATENT OFFlCE.

MOLDING POWDER AND PROCESS OF" MAKING THE SAME Arthur M. Howald, Toledo, Ohio, assignor, by mesne assignments, to Plaskon Company, Incorporated, a corporation of Delaware No Drawing. Application November 10, 1930, Serial No. 494,693. Renewed August 21, 1936 16 Claims. (Cl. 106-22) This invention relates to molding powders and denser action comes into play than is the case processes of making the same; and it comprises with the artificial resins now largely used in radio as a new composition of matter a particular dry sets. composition of formaldehyde and urea in mo- In most of the proposed processes urea and a lecular proportions between 1.05:1 and 1.55:1, formaldehyde solution are caused to undergo a 5 said composition being soluble and fusible and in preliminary condensation or reaction at a temthe fused state solidifying or setting to a hard, perature around 100 0.; this being considered glassy, infusible body; and it also comprises a a necessity and considerably higher temperatures dry granular molding powder containing such with pressure have been proposed. Ordinarily,

i0 fusible composition in amount permitting conalso the proportion of formaldehyde to urea is venient molding under heat and pressure and large; the amount of formaldehyde being at least also containing inert matter or filler, such inert equal to that of urea; or, in molecular propormatter being sometimes a previously set matter tions, at least 2:1; In the standard method inlof the same composition and sometimes an orditial condensation is at a high temperature and i5 nary filler such as wood flour; said powder somethen the liquid product is evaporated to a viscous times also containing a modicum of another fusiconsistency; the gelled product being afterwards ble material or of a dye or of both; and it furbaked at 80 C. to give the hard final material. t comprises a method f pr du in a certain From this material, which is a sort of cast cake new dry soluble fusible condensation product of re resenting a highly polymerized material, ar-

urea and formaldehyde wherein formaldehyde tim re d by cutting to shape and dimen- 20 and urea are admixed in a sli h ly a i s l sions. In baking much formaldehyde and water in molecular proportions Somewhat in excess of are driven off and shrinkage is large. With an 121 and materially below 211, admixture being initial molecular ratio of 2:1 about 0.5 molecule at room temperature and the acidity bein M bf formaldehyde or 12 per cent by weight, must narily about 5 t0 6 D and being insllfficient to be disposed of somehow, as I have found, in mak- 2'5 produce reaction with formation of aprecipitate, m the best glassy t 1 Retention of any 811d the Solution is evaporated at a low tempera water or free formaldehyde in the finished article ture, often in the presence of admixed filler; the leads to deterioration. This dissipation of form. urea of the mixture being sometimes replaced aldehyde is not only wasteful but renders m.

in part by another material capable of reaction duction f if ly shrunk stmmless, 30 with formaldehyde, such as thiourea or resorcinol vesicular cast cakes a matter f h dimculty and the filler when used being either previously In the present invention a method is provided set material of the same nature or an ordinary wherein the amount at formaldemde used is filler Such as. Wood flour; all as mm fully hereited to that wanted in the finished materials.

mafter Set forth and as claimed 1 Formaldehyde and urea react together under 35 Many Ways of producing products. from urea .different circumstances to form avariety of prodand formaldehyde useful in the plastic arts have ucts of reactions which are mostly complex and been proposed and occasionally artlcles of little understood and which involve condensation genent prollemes g gf It with exit of H20 and polymerization, the formal- 4Q owever no prove prac ca on a commerc a I scale to produce regularly hard high grade fingg g z iggg ggi i f s z igg figg 'ished articles free of internal stresses and strains 1 products as combinations of urea and formaldeor of a sufficiently stable chemical character to withstand sunlight and atmospheric influences hyde and this will be done hereinafter Very many products of widely different properties can 5 At their best, clear, hard, glassy materials can be made by using different catalysts and by varyf h adva ta eous ro be made having most 0 t e n g p p ing proportions and conditions; but not many 1 e I fi f gi i j ggfi gigggizfi j figgfii 2;? have been extensively investigated. For the most a Their color is water white and can be changed part these products are amorphous insoluble P iby dyes to any delicate pastel shade that is cipitates, or gels. Combination takes place with wanted. Where a filler is used the material is a considerable evolution of e y as e t; and much like porcelain. With these high grade the products are little reactive. In a general way articles the electrical properties are excellent; it may be Said that combination n al al ne S and particularly the dielectric properties. There lution tends to the production of soluble simple is much less power loss in situations where a concondensation products while in acid media reac- 55 tion goes further, giving the stated insoluble bodies as precipitates or gels.

One product which represents the maximum saturation of urea with formaldehyde is dimethylol urea CO (NH.CH2OH) 2; formed by the union of formaldehyde and urea in a 2 1 molecular proportion. This is a water soluble crystalline body which can be formed under alkaline conditions where the solution contains 2 mols or more of formaldehyde for each mol. of urea. In acid solution the ratio must be greater than 2 1 to force a formation of dimethylol urea. Dimethylol urea when dry or exposed to heat tends to lose formaldehyde and water with formation of indefinite, infusible end products. Under alkaline and refrigerative conditions, in the presence of only one molecule of formaldehyde for each molecule of urea, that is, in a 1:1 ratio, monomethylol urea (CO.NH2NH.CH2OH) is produced. -'Ihis is also a water soluble crystalline body. It will be noted that both the bodies are unpolymerized, being each formed from a single molecule of urea and they are of simple definite constitution. Both are laboratory products and neither has developed any utility for practical purposes.

The results are quite different in acid media. On the addition of any substantial amount of urea to commercial 35-40 per cent aqueous formaldehyde 'solution, which is always acid with a pH below 4, reaction ensues with development of heat which may be suiiicient to bring the liquid to a boiland cause production of precipitates or irreversible gels unless the proportion of formaldehyde is considerably in excess of 2: 1. Not much is known of the ill-defined amorphous insoluble materials (Dixon, J. Lond, Chem. Soc. 1918, vol. 113, page 238) so formed but two are alleged to, be methylene urea and Goldschmidts compound, (C5H1003N4) nthe value of n being unknown. The value of n depends on the degree of polymerization of the precipitate or gel and this probably varies considerably under difierent conditions. The formula represents as a least value the product of the interaction of formaldehyde and urea in the molecular ratio of 3 2; aproduct which should contain about 32 per cent nitrogen. Precipitates containing about this amount of nitrogen can be obtained quite generally from 'acid solutions containing formaldehyde and urea in these proportions; and about this percentage of nitrogen occurs in some of the hard glassy final products of the prior art. I believe therefore, I have some warrant for assuming that these vitreous bodies represent Goldschmidts compound as a still further polymerized continuum.

I have found in operating at the ordinary room temperature with acid solutions of restricted acidity that on addition of urea while condensation with evolution of heat takes place there is no separation of Goldschmidts compound as a precipitate or gel if the temperature does not rise too much and that solutions are formed of sufficient stability to withstand evaporation at low temperatures to produce a dry product. This dry product on heating however undergoes polymerization; it at first fuses and then sets to a continuum. The proper acidity for operation depends on the temperature and with effective cooling to prevent rise in temperature it may go as high as pH 4. Slower interaction but safer operation is given with less acidity-say between pH 5 and pH 6. With pH 6 the liquid is more mobile and easier handled in evaporation and in impregnating paper and fillers precedent to evaporation. On the other hand, with pH 5 the dry product sets somewhat quicker under heat and pressure. It is sometimes convenient to work with a pH of 6 up to the time of drying and then develop a little greater acidity, say pH 5 or even pH 4. With either pH value and with the reaction temperature kept below say 60 0., at all times, there is no development of insolubles in reaction which will not go into solution again on slightly warming. High temperatures are more dangerous near the beginning of the action than later. Reaction at an average temperature of, say, 30 C. requires some hours for completion. Four hours are sufflcient but it is often convenient to let the liquid mixture made by dissolving urea in partially neutralized commercial formaldehyde solution stand over night. Neutralization to secure the desired pH may be with any suitable base. Triethanolamine has some advantages and is recommended, triethanolamine being an organic amine non-active with formaldehyde. It leaves no mineral salines in the composition. Guanidin and other organic bases may be used. However, in the small amounts necessary, potash and soda do no harm.

The formaldehyde and urea may be mixed in Goldschmidts proportions of 3:2 molecules or, by weight, 3 parts of CHzO to 4 parts of COZN2H4; using commercial aqueous formaldehyde solution and dissolving in it the proper amount of urea. Alkyl and aryl substituted ureas may be used in lieu of, or in partial replacement of ordinary urea; ethyl urea or benzyl urea for example; using the same ratios. Thiourea may be used and is often convenient as an admixture with ordinary urea.

Goldschmidts proportions are 1.5:1, but this ratio permits of some variation. The best results are obtained in the range 1.55:1 and 1.05:1. Final glassy articles of the best stability are obtained with proportions somewhat below Goldschmidts 1.5:1 ratio, say about 1.321. This is the initial proportion and in the dry condensation product the formaldehyde is somewhat less, due to a slight loss of formaldehyde as gas during evaporation. This loss however is small. The nitrogen content of the finished material is about 33 to 35 per cent. The yield of product depends on the particular ratios of formaldehyde and urea used. With a ratio of 1.221, the yield of finished product is 1.35 times the dry weight of urea employed. With an initial ratio of 1.5:1, the yield of finished product is ordinarily about 1.45 times the dry weight of urea employed.

A liquid reaction product with about 50 per cent solid and at a pH of 6 can be readily evaporated and dried by spraying into a current of warm air. The physical moisture present in the dried product may be brought as low as 2 per cent. Liquid materials made with a pH of 5 are somewhat more gummy and do not spray as well but may be brought to dryness in other ways. However made, the dried material is water so]- uble unless a temperature of 50 or 60 C. is exceeded during preparation or drying. In this event however unless there has been undue heating it is still readily dispersible in water. The spray dried material is a powder which is convenient for packaging and storing. v

The dry material can be packaged and stored indefinitely, undergoing no alteration in keeping. It is convenient for use in preparing a cold water varnish or lacquer. 0n addition of about its own weight of water it forms a thick solution readily brushed and sprayed. Applied to a sur- .face a film at first dries and then polymerizes,

giving a lustrous water resistant lacquer coating. The dried material may be mixed with neutral pigments to give a cold water paint.

The dry material may be physically mixed with fillers, such as wood flour to produce a molding powder.

Where compositions containing fillers are de sired for molding it is however most convenient to incorporate the filler with the liquid prior to evaporation. The moist mixture so made may be directly dried in an air current producing a dried mixture of reaction product and filler which is of the same order of fineness as that of the filler used; there being no substantial sticking or agglomeration during drying. After drying the material may be packaged and stored indefinitely. When wanted for. use a suitable amount is weighed into a mold and heat and pressure applied. Usually a temperature around 140 C. and a pressure of one ton per square inch are used. At this temperature and under this pressure there is no substantial evolution of volatiles. There is not enough to cause vesiculation, blistering or pitting. The molded article when cold is free of stresses and strains and withstands an accelerated test of boiling with water for one hour. In the absence of dye its color is that given by the filler. With mineral fillers, such as blanc fixe, the article resembles porcelain.

In another advantageous application of my new condensation product the cold liquid made as previously described is used to saturate paper or fabric and the paper or fabric dried at a low temperature as before. A number of sheets of paper or fabric so treated can be assembled and hot pressed to give a laminated material of attractive properties which can be used for radio panels and similar purposes. It may be of any color desired.

Where clear or translucent articles consisting wholly of the final reaction product are desired, they may be secured by the artifice of using fine ground, previously hardened condensation product as a filler. For example, flawed pieces from prior operations may be ground to a fine powder and mixed with the liquid cold condensation product as a filler; the mixture being dried as before. Or, Goldschmidts product in granular form, obtained by precipitation, after washing and drying, may be used as a filler in admixture with the cold liquid condensed product described.

Shaped or partially shaped molded articles of paper pulp or other fibrous materials may be impregnated with the liquid, dried and/or baked. Pressure in the setting operation is not absolutely necessary although when practicable it is always advantageous.

In the production of sheet material for fancy boxes, radio panels, etc., the initial liquid material is taken up in paper, one or more layers of paper assembled and the whole hot pressed.

Other materials than ureas can sometimes be used in admixture and are sometimes convenient as plasticizers; such as resins, castor oil, etc. Since these materials are insoluble in water, however, they are to be added to the dried granular material as physical admixtures. An admixture of a little of the resin known as Glyptal carrying some phthalic anhydrid in solution is particularly useful. This resin does not melt until molding temperatures are reached and when it does melt it liberates phthalic anhydrid to increase the acidity or the mixture; something which is advantageous. Other advantageous substances carrying masked acidity are betabromcinnamic acid and its salts which at molding temperatures liberate free HBr.

Materials made under the present invention are permanent and long lived, withstanding an exposure to atmosphere, sunlight and most chemical reagents. Even hot acids, unless tolerably concentrated do not affect them. They withstand an accelerated test of boiling in water for one or more hours.

Somewhat more resistance to boiling wate and atmospheric actions may be obtained by incorporating a little resorcinol and formaldehyde in the original solution; these additions being best in the molecular ratio of 1 to 2. The resorcinol addition, however, gives a somewhat darker color to the final product and is therefore not desirable when light pastel shades are wanted.

It is convenient to keep a white stock powder with other smaller stocks of intensely dyed powders in various colors for admixture therewith when any particular color is desired. Provision of these differentlycolored stocks also makes convenient the production of articles of variegated color.

In another and copending application Serial No. 484,719, filed September 26, 1930, I have described and claimed another method of operation in which a preliminary heating for condensation is not used. Theflnal purpose, the production of a molding powder, is the same as here but the mechanism of action is quite different. In the acknowledged application urea is condensed with a relatively large amount of formaldehyde, about 2 molecules of the latter for one of the former, condensation being in the cold. After the condensation is effected a further amount of urea is added. In the present invention all the urea used is added to all the formaldehyde in the beginning. The condensation or chemical reaction between the two therefore takes another course. Excellent molding powders may be made in either way.

The dried primary reaction product may be softened by heat and forced into molds to give shaped articles; the casting being kept hot merely long enough for polymerization. There being no substantial loss of volatiles there is little shrinkage or production of internal strains. This method is convenient in producing bar stock for lathe work; or articles to be finished mechanically, lenses for example.

It is considered that on the whole it is best to maintain an average temperature of about 30 C. during the initial action of urea and formaldehyde on each other. The first effect of adding urea is to chill the liquid and it is sometimes advisable to heat the formaldehyde solution to a temperature sufficiently high above 30 C. to compensate for the chilling effect of the urea. In the course of the reaction heat is developed and with the solution at any time at a. temperature overnight is convenient.

abouts the arrested polymerization now takes place and solid materials are formed.

The procedure described ante may be summarized in a step by step manner as follows:

A somewhat acid commercialformaldehyde solution is partially neutralized and adjusted to a pH of about 6 by the addition of a suitable amount of triethanolamine. Sufficient urea is dissolved in the so-treated formaldehyde to give a molar ratio of formaldehyde to urea of 1.5:1. The solution is maintained at about room temperature (20-30 C.) until the formaldehyde and urea have combined. Permitting the solution to stand Then the reaction is arrested by drying at low temperatures (below 60 C.). This may be effected by mixing sumcient paper pulp with the mobile solution of initial reaction product, to give a moist mass of paper pulp impregnated with reaction product and then drying the moist mass in a current of air, the drying temperature being below 60 C. A satisfactory molding composition is obtained.

It is advantageous to adjust the acidity of the solution to a pH of 4 to 5, just prior to drying.

A substance developing acidity during hot pressing may be advantageously added to the dried molding composition or powder. For this purpose, the beta-bromcinnamic acid or other materials carrying masked acidity, mentioned ante, may be used.

The molding composition and powders thus prepared are molded at around 140 C. and under pressure of about one ton per square inch. Under those conditions, there is no substantial evolution of volatiles; evolution of volatiles sufficient to cause vesiculation, blistering or pitting. The molded articles are high grade, stable products, withstanding an accelerated test of boiling with water for one hour.

What I claim is:

1. As an improvement in the manufacture of hard, molded, permanent, stable, infusible articles from urea and formaldehyde, the improved process which comprises instituting a reaction between urea and formaldehyde in the molar ratio of formaldehyde to mm between 1.55:1 and 1.05:1 in a faintly acid aqueous solution of pH around 6, to produce a primary reaction product, allowing the reaction to go forward at room temperature for a time until the urea has combined with the formaldehyde, arresting the reaction while the primary products are still water-soluble and the solution of primary reaction products is still a mobile liquid, by evaporating the water from the liquid solution at a temperature insufficient to produce any substantial resiniflcation until a dry, solid, fusible, primary formaldehydeurea reaction product containing not more than 2 per cent physical moisture is obtained, said drying temperature not exceeding 60 C. and then completing the reaction in a hot mold under the influence of heat and pressure, to form said stable, infusible articles without substantial evolution of volatiles sufficient to cause vesiculation and blistering.

2. In the manufacture of improved molding compositions containing formaldehyde-urea reaction products, the steps of making a potential resin which comprises mixing together formaldehyde and urea in acid aqueous solution, the molecular proportion of formaldehyde to urea being between 1.05:1 and 1.55:1 and the acidity of said'mixture being between 5 and 6 pH, maintaining the mixture at a relatively low temperature not exceeding 60 C. until a mobile reaction solution containing an initial water-soluble reaction product is formed and arresting the reaction by mixing the slightly acid solution of initial reaction product so obtained with sufficient fibrous cellulosic filler to produce a moist mass of impregnated filler and evaporating/oil the contained water, from the slightly acid moist mass so produced, at a temperature not exceeding 60 C. to recover a substantially dry solid molding composition capable of being molded under heat and pressure at a temperature of about 140 C. and a pressure of 1 ton per square inch without substantial liberation of volatiles sufllcient to cause vesiculation and blistering.

3. The process of claim 2 wherein said reaction temperature is room temperature.

4. The process of claim 2 wherein an acid commercial formaldehyde solution is partially neutralized with an organic amine to obtain a pH between 5 and 6, the said organic amine being non-reactive with formaldehyde, urea is dissolved in said solution and the mixture is permitted to stand undisturbed for several hours thereby obtaining an initial reaction going forward to a substantial extent but without production of gelling or development of insolubles. thereby producing a mobile solution of initial water-soluble formaldehyde-urea condensation product, free of mineral salines and capable of impregnating and saturating fibrous cellulosic fillers.

5. The process of claim 2 wherein. the ratio of formaldehyde to urea is 1.3:1, the acidity is about pH 6 and the reaction is effected at room temperatures 6. The process of claim 1 wherein the said solution of initial reaction product is adjusted to a pH between 4 and 5 just prior to arresting the reaction by drying and the dry acid-reacting mixture so obtained is resinified under heat and pressure, the resiniflcation being at temperatures around 140 C. under a pressure of about 1 ton per square inch. 7

7. In the process of claim 2, facilitating evaporating off the contained water and the preparation of a molding powder wherein the slightly acid liquid reaction solution is admixed with an absorbent cellulosic filler in amount sufllcient to produce a moist mass of impregnated fillerbyincreasing the acidity to a point between 4 and 5 pH just prior to drying and then drying the moist mass at a temperature below 60 C. in a current of warm air.

8. An improved molding powder comprising a substantially dry composition of an absorbent, fibrous filler impregnated with a potential resin having formaldehyde and urea residues combined in a ratio between 1.05:1 and 1.55:1, said potential resin being an arrested low temperature, acidcondensed reaction product of formaldehyde and urea in said ratio produced at a low temperature not exceeding 60 C. in a faintly acid aqueous solution having a pH between 4 and '7, and being soluble, fusible and substantially free of volatiles, said potential resin on exposure to heat at molding temperature, first flowing under the pressure and then resinifying without substantial evolution of volatiles sufficient to cause vesiculation and blistering to produce a hard infusible stable resin, the two actions being consecutive and rapid at temperatures around 140 C. under pressure of about 1 ton per square inch.

9. The molding powder as set forth in claim 8 in which the filler is a fibrous cellulosic filler.

10. The molding powder as set forth in claim 8 in which the filler is paper pulp.

11. An improved substantially dry molding composition comprising a body of paper pulp impregnated and saturated with an arrested initial reaction product of formaldehyde and urea, said body of paper pulp being a preshaped and formed body, said arrested initial reaction product being a potential resin having formaldehyde and urea residues combined in a ratio between 1.05:1 and 1.55:1, being an arrested, low temperature, acidcondensed, initial reaction product of formaldehyde and urea in said ratio, being soluble, fusible and substantially free of volatiles, said potential resin further being capable of heat-hardening without substantial liberation of volatiles at temperatures around 140 C. and being in said molding composition capable, when under a temperature around 140 C. and pressure of one ton per square inch, of flowing suiliciently to become compacted and dense, prior to heat-setting.

12. In the manufacture of molding powders, the improved process of preparing dry, fusible, rapidly heat-setting powders containing arrested initial reaction products of ureaand formaldehyde which comprises dissolving urea in slightly acid aqueous solution of formaldehyde at a pH value between 4 to 7, the molecular ratio of formaldehyde to urea being in the range between 1.05:1 and 1.55:1, maintaining the mixture at a temperature not exceeding 30 C. for a time sufficient to effect substantial reaction without formation of a precipitate, mixing the slightly acid mobile solution of initial formaldehyde-urea reaction product so obtained with a sufficient amount of finely divided cellulosic filler toproduce a moist mass and then drying the slightly acid moist mass of cellulosic filler, impregnated with the said solution, at a temperature not exceeding 60 C., in

a current of warm air until a substantially dry molding powder capable of being molded under heat and pressure, without the liberation of volatiles sufficient to cause vesiculation and blistering at temperatures around 140 C. and under pressures of about 1 ton per square inch.

13. As an improvement in the manufacture of pressure-shaped, heat-hardened, molded articles which are stable, insoluble and infusible' from molding compositions containing fusible formaldehyde-urea reaction products having formaldehyde and urea combined in substantially the same molar ratio in which they are to be fixedly combined in the final infusible molded article, the improvement which comprises partially neutralizing the acidity of a commercial aqueous formaldehyde solution with an organic amine capable of permanently adjusting the said acidity to between a pH of 4 to 7 but incapable of reacting with the formaldehyde content thereof, adding urea in the proportion of 1 molecule to every 1.5 molecules of CHzO present, allowing the mixture to stand at a temperature between 20 and 30C.

until the initial reaction is substantially completed and a slightly acid mobile liquid is produced, adding paper pulp in a proportion suiTicient to make a moist, open textured mass, drying the moist material having a pH between 4 and 5 at temperatures not exceeding 60 C. until substantially all the water is removed and com minuting the dried material to a state of fineness suitable for a molding powder.

14. An improved molding composition, said composition being dry and comprising in addition to other ingredients, an arrested, acid-condensed, initial low temperature reaction product of urea and formaldehyde, said reaction product having formaldehyde and urea combined in approximately the ratio of 1.5:1 and being a soluble, fusible, heat-setting body, the reaction product in said molding compositions being capable of softening and of then heat-hardening, said dry molding composition being capable, at temperatures around 140" C. under pressures of about 1 ton per square inch, of conversion into solid, insoluble, infusible, stable, molded articles, without liberation of substantial amounts of volatiles.

15. In the manufacture of articles from dry molding compositions containing fusible, substantially volatile free urea-formaldehyde condensation products, having formaldehyde and urea combined in a molar ratio substantially the same as that in which they are to be fixedly combined in the final molded article the process steps which comprises forming, in a controlled manner, at temperatures not exceeding 60 C. in an aqueous solution having a pH between 4 and 7, an initial reaction product of urea and formaldehyde having formaldehyde and urea combined in a ratio of approximately 1.5: 1 and then arresting reaction and isolating said initial reaction prodnot without substantial polymerization or resinification by removing the water and other volatiles at relatively low temperatures not exceeding 60 C. prior to the development of insolubility.

16. As an improvement in the manufacture of urea-formaldehyde condensation products by a process wherein urea and formaldehyde are reacted together in aqueous solution ajad reaction is arrested by drying at low temperatures to recover a dry, fusible solid product, the method which comprises restricting the ratio of formaldehyde to urea to approximately 1.5:1, adjusting the acidity of the'aqueous reaction medium to approximately pH 6 and arresting the'reaction after it has gone forward to a substantial extent but before insolubility or gelling occur, by evaporating the water and other uncombined volatiles at temperatures not exceeding 60 C. until dry solid compositions are obtained capable of being 

